WO2024080837A1 - Batterie secondaire - Google Patents

Batterie secondaire Download PDF

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Publication number
WO2024080837A1
WO2024080837A1 PCT/KR2023/015867 KR2023015867W WO2024080837A1 WO 2024080837 A1 WO2024080837 A1 WO 2024080837A1 KR 2023015867 W KR2023015867 W KR 2023015867W WO 2024080837 A1 WO2024080837 A1 WO 2024080837A1
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WO
WIPO (PCT)
Prior art keywords
electrode assembly
secondary battery
electrolyte
pouch
battery
Prior art date
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PCT/KR2023/015867
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English (en)
Korean (ko)
Inventor
김현진
위연화
김창호
김선욱
김재민
Original Assignee
주식회사 엘지에너지솔루션
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Priority claimed from KR1020230136858A external-priority patent/KR20240052696A/ko
Publication of WO2024080837A1 publication Critical patent/WO2024080837A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/141—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against humidity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
    • H01M50/673—Containers for storing liquids; Delivery conduits therefor
    • H01M50/682—Containers for storing liquids; Delivery conduits therefor accommodated in battery or cell casings

Definitions

  • the present invention relates to secondary batteries, and more specifically, to secondary batteries with excellent impact resistance.
  • Secondary batteries generally manufacture positive electrodes and negative electrodes by applying electrode active material slurry to the positive electrode current collector and negative electrode current collector, and then stack them on both sides of a separator to form an electrode assembly of a predetermined shape. , It is manufactured by storing the electrode assembly in a pouch and injecting electrolyte.
  • the pouch-type secondary battery is manufactured by performing press processing on a flexible pouch film laminate to form a cup portion, storing the electrode assembly in the cup portion, injecting electrolyte solution, and sealing the sealing portion, and can-type ( Can Type) Secondary batteries are manufactured by placing an electrode assembly in a can made of metal, injecting an electrolyte solution, and then assembling a top cap on the top of the can to seal it.
  • Pouch-type secondary batteries have the advantage of being light in weight, excellent in space utilization, and capable of realizing high energy density using a stacked electrode assembly, but have the problem of being vulnerable to external shock compared to can-type secondary batteries.
  • the present invention is intended to solve the above problems.
  • the size of the electrode assembly and the amount of electrolyte per unit capacity satisfy certain conditions, thereby increasing the friction between the electrode assembly and the battery case (e.g., pouch). It relates to a secondary battery in which separation of the electrode assembly and/or leakage of electrolyte is suppressed even when subjected to external shock or mechanical stress.
  • the present invention provides a secondary battery that includes a battery case including an electrode assembly, an electrolyte, and a receiving portion for accommodating the electrode assembly and the electrolyte, and satisfies the following equation (1).
  • Equation (1) W/S ⁇ 42
  • W is the electrolyte weight per unit capacity of the secondary battery [unit: g/Ah]
  • S is the product of the overall length [unit: m] and the overall width [unit: m] of the electrode assembly. .
  • the secondary battery disclosed herein may include any, part, or all of the features described further below.
  • the secondary battery may be a pouch-shaped battery, a cylindrical battery, a prismatic battery, etc.
  • the secondary battery may be a pouch-shaped battery.
  • the capacity of the secondary battery means the rated capacity of the secondary battery.
  • the secondary battery may have a rated capacity of 50 Ah to 200 Ah, preferably 50 Ah to 150 Ah, and more preferably 60 Ah to 140 Ah.
  • “Rated capacity of secondary battery” refers to the electric capacity developed when a fully charged battery is continuously discharged at 0.33C and reaches the discharge end voltage. At this time, the full charge voltage (charge end voltage) and discharge end voltage may be appropriately selected depending on the type of secondary battery. For example, when the secondary battery is an NCM cell, the rated capacity may be the discharge capacity when the secondary battery is charged to 4.25V and then discharged to 2.5V at 0.33C.
  • “Unit capacity” means 1 Ah.
  • the W may have a unit of g/Ah
  • the S may have a unit of m 2
  • the W/S may have a unit of (g/Ah) ⁇ m -2 .
  • the W may be 2.2 g/Ah or less, preferably 1.5 to 2.2 g/Ah, and more preferably 1.7 to 2.2 g/Ah, and the S may be 0.01 m 2 to 0.2 m 2 , 0.02 m 2 to 0.09 m 2 , preferably 0.03m 2 to 0.08m 2 , more preferably 0.03m 2 to 0.75m 2 .
  • the weight of the electrolyte in the secondary battery refers to the amount of electrolyte remaining in the secondary battery after the activation process. Accordingly, the total weight of the electrolyte may refer to the total weight of the electrolyte present after completion of manufacturing or during operation of the secondary battery.
  • the W/S (unit: (g/Ah) ⁇ m -2 ) is, for example, 0.1 (g/Ah) ⁇ m -2 to 42 (g/Ah) ⁇ m -2 , 1 (g/Ah) ) ⁇ m -2 to 42(g/Ah) ⁇ m -2 , 5(g/Ah) ⁇ m -2 to 42(g/Ah) ⁇ m -2 , 10(g/Ah) ⁇ m -2 to It may be 42(g/Ah) ⁇ m -2 , or 20(g/Ah) ⁇ m -2 to 42(g/Ah) ⁇ m -2 , but is not limited thereto.
  • the W/S (unit: (g/Ah) ⁇ m -2 ) is 30 (g/Ah) ⁇ m -2 to 42 (g/Ah) ⁇ m -2 , more preferably 35 (g /Ah) ⁇ m -2 to 42(g/Ah) ⁇ m -2 .
  • the secondary battery prepares an electrode active material slurry, applies it to a positive electrode current collector and a negative electrode current collector to obtain a positive electrode and a negative electrode, and attaches at least one layer of the positive electrode and at least one layer of the separator between the positive electrode layer and the negative electrode layer. It can be manufactured by stacking the electrode assembly with a separator interposed therebetween, storing the electrode assembly in a battery case such as a pouch, cylindrical can, or square can, and then adding an electrolyte to the electrode assembly.
  • the pouch-type secondary battery presses the pouch film laminate to form a cup with a shape and dimension to accommodate the electrode assembly, then places the electrode assembly in the cup, adds an electrolyte, and then stacks the pouch film. It can be manufactured by sealing along the sealing part of the sieve.
  • a can-type secondary battery can be manufactured by placing an electrode assembly in a metal can, injecting an electrolyte into the can, and sealing the can by mounting a cap on the opening of the can.
  • the can may have a cylindrical or angular shape, such as a rectangle, a cuboid, or a diamond.
  • the electrolyte of the secondary battery will be described later.
  • the electrode assembly of the secondary battery will be described later.
  • the battery case of a secondary battery may be a pouch, and the pouch may be used as a commonly understood concept in the field of secondary battery design and manufacturing.
  • the battery case of the secondary battery may be a can as described herein. At least a portion of the electrolyte may be provided between the electrode assembly and the inner surface of the battery case facing the electrode assembly.
  • the electrode assembly may have a rectangular shape extending in the longitudinal direction on a plane.
  • overall length means the length measured in the longitudinal direction, unless otherwise specified.
  • the width direction of the electrode assembly represents a direction perpendicular to the longitudinal direction, and is disposed on the plane of at least one layer of the anode, cathode, and separator.
  • the full width is a value measured in the width direction unless otherwise specified.
  • the anode layers, cathode layers, and separator may be stacked in a thickness direction perpendicular to both the longitudinal and width directions.
  • flatness may mean a gaze direction parallel to the thickness direction of the electrode assembly.
  • the electrode assembly may be wound along a winding axis parallel to the longitudinal or width direction. Therefore, the other direction of the longitudinal direction and the width direction that is not parallel to the winding axis may be parallel to the circumferential direction of the electrode assembly.
  • the overall length refers to the length of the electrode assembly in the direction of the winding axis in the wound state
  • the overall width refers to the length of the electrode assembly in the direction perpendicular to the winding axis in the wound state.
  • the battery case may be a pouch that can be provided in any manner disclosed herein.
  • the pouch may be formed by pressing at least one cup portion onto a pouch film laminate.
  • the cup portion may be formed as a flat portion protruding outward from the remaining portion of the pouch film laminate.
  • the cup portion may have a tray-like shape.
  • the cup portion may include a flat main surface surrounded by one or more side walls that are integral with the remainder of the pouch film stack.
  • the flat main surface of the cup portion may have a basic shape of a flat rectangle, but the corners may be rounded depending on processing requirements or design.
  • the pouch may have any, some, or all of the features of the pouch described herein, unless otherwise specified or technically inappropriate.
  • the battery case may be a pouch made of a pouch film laminate.
  • the pouch specifically, the pouch film laminate, may include a barrier layer, a base layer, and a sealant layer.
  • the base layer may be disposed on one side of the barrier layer, and the sealant layer may be disposed on the other side of the barrier layer (i.e., the opposite side of the base layer).
  • the base layer, the barrier layer, and the sealant layer may form a pouch film laminate, specifically, a laminated structure.
  • the pouch, specifically the pouch film laminate is press molded (specifically, stretch molded and/or or drawing).
  • the electrode assembly may be accommodated in the one or more cup portions.
  • the at least one cup portion may have a shape and dimension to accommodate the electrode assembly.
  • Components of the pouch may implement any, part, or all of the features disclosed herein, unless otherwise specified or technically inappropriate. Specifically, any one of the base layer, barrier layer, and sealant layer may be implemented as each is described in detail below.
  • the secondary battery may have a rated capacity of 50 Ah to 200 Ah, preferably 50 Ah to 150 Ah, and more preferably 60 Ah to 140 Ah.
  • the electrode assembly may have a substantially rectangular shape in a plane, and a ratio of the overall length to the overall width of the electrode assembly may be 2.5 to 20, 3 to 15, 5 to 10, or 5 to 8.
  • a ratio of the overall length to the overall width of the electrode assembly satisfies the above specific range, it can further contribute to increasing friction without increasing the amount of electrolyte.
  • the electrode assembly may have a total length of 200 mm to 800 mm and an overall width of 40 mm to 200 mm.
  • the electrode assembly may have a total length of 400 mm to 600 mm and an overall width of 50 to 150 mm, and more preferably, the overall length may be 500 mm to 600 mm and an overall width of 50 to 100 mm.
  • the full length and full width may mean the maximum extended length of the electrode assembly in the longitudinal and width directions on a plane, respectively.
  • the weight of the electrode assembly may be 500g to 1500g, preferably 550g to 1450g, and more preferably 600g to 1400g.
  • the weight of the electrode assembly satisfies the above range, high capacity can be realized, and the friction between the electrode assembly and the inner surface of the battery case increases, resulting in excellent impact resistance.
  • the secondary battery according to the present invention may further include at least one fixing member fixed to the outer surface of the electrode assembly by wrapping the electrode assembly in the full width direction.
  • the contact area between the fixing member and the electrode assembly This may be 30% or less, 0 to 30%, 1 to 30%, 5 to 30%, 5 to 25%, or 5 to 20% of the total surface area of the electrode assembly.
  • the fixing member is generally made of a material with a low coefficient of friction, when the area of the fixing member increases, the friction between the electrode assembly and the inner surface of the battery case may decrease. Therefore, when using a fixing member, it is desirable to suppress a decrease in friction force by setting the contact area between electrode assemblies to 30% or less.
  • the battery case may be a pouch-type case, and the pouch-type case includes a barrier layer, a base layer formed on one side of the barrier layer, and a sealant layer formed on the other side of the barrier layer, and is oriented in one direction. It may be a pouch including at least one curved cup portion, and an electrode assembly and an electrolyte may be accommodated in the cup portion of the pouch.
  • the friction force between the electrode assembly and the inner surface of the battery case may be 15 kgf or more, preferably 15 kgf to 40 kgf, and more preferably 17 kgf to 35 kgf.
  • the friction force between the electrode assembly and the inner surface of the battery case can be measured as follows. Cut a part of the battery case, hold the positive tab with a jig with a wire connected to it, connect the wire to a universal testing machine (UTM), and pull it at a constant speed, for example, 100 mm/min, and measure the force ( Force) can be measured and evaluated as the friction between the electrode assembly and the inner surface of the battery case.
  • UPM universal testing machine
  • the electrode assembly may have an overall length of 0.2 m to 0.8 m, an overall width of 0.05 m to 0.15 m, and an electrolyte weight per unit capacity of 1.0 to 2.8 g/Ah.
  • W/S may be 30 (g/Ah) ⁇ m-2 to 42 (g/Ah) ⁇ m-2.
  • the electrode assembly may have an overall length of 0.3 m to 0.8 m, an overall width of 0.06 m to 0.12 m, and an electrolyte weight per unit capacity of 1.2 to 2.5 g/Ah. In this case, W/S may be 30 (g/Ah) ⁇ m-2 to 42 (g/Ah) ⁇ m-2.
  • the electrode assembly may have an overall length of 0.4 m to 0.6 m, an overall width of 0.07 m to 0.11 m, and an electrolyte weight per unit capacity of 1.5 to 2.4 g/Ah.
  • W/S may be 30 (g/Ah) ⁇ m-2 to 42 (g/Ah) ⁇ m-2.
  • the present invention can provide a secondary battery including an electrode assembly, an electrolyte, and a battery case.
  • the electrode assembly may have a surface area of 0.01 to 0.2 m 2 , and the total weight of the electrolyte may be 440 g or less.
  • the battery case can accommodate an electrode assembly and an electrolyte.
  • the electrode assembly, electrolyte, and battery case may be configured such that the frictional force between the electrode assembly and the inner surface of the battery case is 15 kgf or more.
  • the surface area of the electrode assembly may be the product of the full length and the full width.
  • the surface area of the electrode assembly may be 0.02 m 2 to 0.08 m 2 , or 0.03 m 2 to 0.07 m 2 or 0.04 m 2 to 0.06 m 2 .
  • the friction between the electrode assembly and the battery case increases significantly compared to the prior art, and this causes the electrode assembly to break away in the event of an external impact. And/or electrolyte leakage can be suppressed to achieve excellent impact resistance.
  • FIG. 1 is an exploded perspective view of a secondary battery according to an embodiment of the present invention.
  • Figure 2 is a diagram for explaining the configuration of a pouch according to one embodiment.
  • electrolyte remaining after impregnating the electrode assembly may remain on the surface of the electrode assembly and the inner surface of the battery case. Since the electrolyte has wet characteristics, if electrolyte is present on the inner surface of the battery case and the surface of the electrode assembly, the electrode assembly and the battery The friction between the inner surfaces of the case is reduced, which further increases the flow of the electrode assembly upon external impact. When the total amount of electrolyte in the secondary battery increases, the amount of electrolyte remaining inside the electrode assembly and the battery case increases, which further reduces friction. Therefore, in terms of impact resistance, the smaller the amount of electrolyte in the secondary battery, the better. However, if the amount of electrolyte is too small, the capacity of the secondary battery may be adversely affected and the operability and lifespan of the secondary battery may be reduced.
  • the present inventors have conducted repeated research to develop a secondary battery that can achieve excellent both electrochemical performance and impact resistance of the battery.
  • the electrode assembly It was found that the friction between the battery case and the battery case is greatly increased compared to the prior art, and as a result, damage to the battery case due to separation of the electrode assembly during external impact is suppressed, making it possible to minimize the degradation of electrochemical properties while realizing excellent impact resistance.
  • the present invention has been completed.
  • the secondary battery according to the present invention includes a battery case including an electrode assembly, an electrolyte, and a receiving portion for accommodating the electrode assembly and the electrolyte, and is characterized by satisfying the following equation (1).
  • Equation (1) W/S ⁇ 42
  • the unit of W/S in equation (1) above is (g/Ah) ⁇ m-2.
  • the W (unit: g/Ah) is the weight of electrolyte per unit capacity of the secondary battery, and can be measured by dividing the total weight of electrolyte in the secondary battery (unit: g) by the rated capacity of the secondary battery (unit: Ah). Meanwhile, the total weight of the electrolyte in the secondary battery refers to the total weight of the electrolyte remaining in the secondary battery after the activation process.
  • the W/S (unit: (g/Ah) ⁇ m -2 ) is 42 (g/Ah) ⁇ m -2 or less, 0.1 (g/Ah) ⁇ m -2 to 42 (g/Ah) ) ⁇ m -2 , 1(g/Ah) ⁇ m -2 to 42(g/Ah) ⁇ m -2 , 5(g/Ah) ⁇ m -2 to 42(g/Ah) ⁇ m -2 , It may be 10(g/Ah) ⁇ m -2 to 42(g/Ah) ⁇ m -2 , or 20(g/Ah) ⁇ m -2 to 42(g/Ah) ⁇ m -2 , but is limited thereto. It doesn't work.
  • the W/S (unit: (g/Ah) ⁇ m -2 ) is 30 (g/Ah) ⁇ m -2 to 42 (g/Ah) ⁇ m -2 , more preferably 35 (g /Ah) ⁇ m -2 to 42(g/Ah) ⁇ m -2 .
  • W/S is 42(g/Ah) ⁇ m -2 or less, the friction between the electrode assembly and the inner surface of the battery case (for example, the bottom surface of the cup of the pouch) in contact with the electrode assembly greatly increases, resulting in When external shock is applied, separation of the electrode assembly is minimized, thereby minimizing electrolyte leakage due to damage to the battery case.
  • the W may vary depending on the size of the electrode assembly, but for example, 2.2 g/Ah or less, preferably 1.5 g/Ah to 2.2 g/Ah, more preferably 1.7 g/Ah to 2.2 g. It could be /Ah. If W is too large, the effect of increasing friction between the electrode assembly and the inner surface of the battery case is minimal, and if W is too small, battery performance may deteriorate due to insufficient electrolyte during battery operation.
  • S is the cross-sectional area of the electrode assembly, which is a value obtained by multiplying the full length and full width of the electrode assembly.
  • the full length and full width are measured in m units.
  • the S may be, for example, 0.02 to 0.09 m 2 , preferably 0.03 to 0.08 m 2 , and more preferably 0.03 to 0.75 m 2 . If S is too small, the battery capacity decreases and the effect of increasing friction between the electrode assembly and the battery case is minimal, and if S is too large, there is a greater risk of accidents when a stability issue occurs.
  • the secondary battery may have a rated capacity of 50 Ah to 200 Ah, preferably 50 Ah to 150 Ah, and more preferably 60 Ah to 140 Ah. When the rated capacity of the secondary battery satisfies the above range, a high capacity secondary battery can be implemented.
  • the secondary battery according to the present invention may be a pouch-type secondary battery.
  • the battery case includes, for example, a barrier layer, a base layer formed on one side of the barrier layer, and a sealant layer formed on the other side of the barrier layer, and at least one cup portion indented in one direction. It may be a pouch containing an electrode assembly and an electrolyte in the cup portion of the pouch.
  • the friction force between the electrode assembly and the inner surface of the battery case is 15 kgf or more, preferably 15 kgf to 40 kgf, more preferably It is high at 17kgf to 35kgf, which minimizes damage to the pouch as there is little separation of the electrode assembly due to external impact, and this results in excellent impact resistance.
  • the friction force between the electrode assembly and the inner surface of the battery case can be measured by the following method.
  • the secondary battery according to the present invention has high friction between the electrode assembly and the battery case, minimizing separation of the electrode assembly during external impact, and thus has excellent impact resistance.
  • electrolyte leakage does not occur when a crash shock test is performed under a crash condition of 133.7G ⁇ 15.8ms. That is, the secondary battery according to the present invention has an electrolyte leakage amount of 0 after a crash shock test under a crash condition of 133.7G ⁇ 15.8ms.
  • the crash shock test can be performed by mounting the battery to be measured on a jig of drop shock equipment, letting the battery fall freely from a certain height, and then determining whether the battery is damaged.
  • the free fall height is set in consideration of the collision condition (acceleration ⁇ duration time) to be measured.
  • the impact energy in the collision condition to be measured can be converted into potential energy, and then the free fall height can be set by calculating the height that can have the converted potential energy by considering the weight of the battery to be measured. Meanwhile, damage to the battery can be evaluated by whether electrolyte leaks or not.
  • FIG. 1 is an exploded perspective view of a pouch-type secondary battery, which is an example of a secondary battery according to the present invention
  • FIG. 2 is a cross-sectional view of a pouch film laminate.
  • the pouch 100 is a battery case for accommodating an electrode assembly and an electrolyte, and includes a barrier layer 20, a base layer 10 formed on one side of the barrier layer, and a sealant layer 30 formed on the other side of the barrier layer. ) and includes at least one cup portion (receiving portion) indented in one direction.
  • the pouch 100 has flexibility, and a pouch film laminate in which a base layer 10, a barrier layer 20, and a sealant layer 30 are sequentially laminated is inserted into a press molding device, and the pouch is formed. It can be manufactured by applying pressure to a portion of the film laminate with a punch and stretching it to form a cup portion that is indented in one direction.
  • the base layer 10 is disposed on the outermost layer of the pouch to protect the electrode assembly from external shock and electrically insulate it.
  • the base layer 10 may be made of a polymer material, for example, polyethylene, polypropylene, polycarbonate, polyethylene terephthalate, polyvinyl chloride, acrylic polymer, polyacrylonitrile, polyimide, polyamide, cellulose. , aramid, nylon, polyester, polyparaphenylenebenzobisoxazole, polyarylate, and Teflon.
  • a polymer material for example, polyethylene, polypropylene, polycarbonate, polyethylene terephthalate, polyvinyl chloride, acrylic polymer, polyacrylonitrile, polyimide, polyamide, cellulose. , aramid, nylon, polyester, polyparaphenylenebenzobisoxazole, polyarylate, and Teflon.
  • the base layer 10 may have a single-layer structure or a multi-layer structure in which different polymer films 12 and 14 are stacked, as shown in FIG. 2 .
  • an adhesive layer 16a may be interposed between the polymer films.
  • the base layer 10 may have a total thickness of 10 ⁇ m to 60 ⁇ m, preferably 20 ⁇ m to 50 ⁇ m, and more preferably 30 ⁇ m to 50 ⁇ m.
  • the thickness includes the adhesive layer.
  • durability, insulation, and moldability are excellent. If the thickness of the base layer is too thin, durability decreases and damage to the base layer may occur during the molding process. If it is too thick, moldability may decrease, the overall thickness of the pouch increases, and the battery storage space decreases, lowering the energy density. may deteriorate.
  • the base layer 10 may have a laminated structure of a polyethylene terephthalate (PET) film and a nylon film.
  • PET polyethylene terephthalate
  • nylon film is disposed on the barrier layer 20 side, that is, on the inside, and the polyethylene terephthalate film is disposed on the surface side of the pouch.
  • PET Polyethylene terephthalate
  • the adhesiveness with the aluminum alloy thin film constituting the barrier layer 20 is weak and the stretching behavior is also different. Therefore, when the PET film is placed on the barrier layer side, the base layer and the barrier layer are separated during the molding process. Peeling may occur, and the barrier layer may not be stretched uniformly, which may cause problems with reduced formability.
  • the nylon film since the nylon film has similar stretching behavior to the aluminum alloy thin film constituting the barrier layer 20, the formability improvement effect can be obtained when the nylon film is placed between polyethylene terephthalate and the barrier layer.
  • the polyethylene terephthalate film may have a thickness of 5 ⁇ m to 20 ⁇ m, preferably 5 ⁇ m to 15 ⁇ m, more preferably 7 ⁇ m to 15 ⁇ m, and the nylon film may have a thickness of 2010 ⁇ m to 40 ⁇ m, Preferably it may be 2010 ⁇ m to 35 ⁇ m, more preferably 2515 ⁇ m to 25 ⁇ m.
  • the thickness of the polyethylene terephthalate film and the nylon film satisfies the above range, excellent moldability and rigidity after molding are exhibited.
  • the barrier layer 20 is used to secure the mechanical strength of the pouch 100, block gas or moisture from entering the secondary battery, and prevent electrolyte leakage.
  • the barrier layer 20 may have a thickness of 40 ⁇ m to 100 ⁇ m, more preferably 50 ⁇ m to 80 ⁇ m, and more preferably 60 ⁇ m to 80 ⁇ m.
  • the barrier layer thickness satisfies the above range, formability is improved and the molding depth of the cup portion is increased or cracks and/or pinholes are less likely to occur even when molding two cups, thereby improving resistance to external stress after molding.
  • the barrier layer 20 may be made of a metal material, and specifically, may be made of an aluminum alloy thin film.
  • the aluminum alloy thin film includes aluminum and metal elements other than aluminum, such as iron (Fe), copper (Cu), chromium (Cr), manganese (Mn), nickel (Ni), magnesium (Mg), and silicon. It may include one or two or more types selected from the group consisting of (Si) and zinc (Zn).
  • metal elements other than aluminum such as iron (Fe), copper (Cu), chromium (Cr), manganese (Mn), nickel (Ni), magnesium (Mg), and silicon. It may include one or two or more types selected from the group consisting of (Si) and zinc (Zn).
  • the aluminum alloy thin film may have an iron (Fe) content of 1.2 wt% to 1.7 wt%, preferably 1.3 wt% to 1.7 wt%, and more preferably 1.3 wt% to 1.45 wt%.
  • Fe iron
  • the iron (Fe) content in the aluminum alloy thin film satisfies the above range, the occurrence of cracks or pinholes can be minimized even when the cup portion is formed deeply.
  • the sealant layer 30 is bonded through heat compression to seal the pouch, and is located in the innermost layer of the pouch film laminate 1.
  • sealant layer 30 is the surface that comes into contact with the electrolyte and electrode assembly after the pouch is molded, it must have insulation and corrosion resistance. It must completely seal the interior to block material movement between the inside and the outside, so it must have high sealing properties. .
  • the sealant layer 30 may be made of a polymer material, for example, polyethylene, polypropylene, polycarbonate, polyethylene terephthalate, polyvinyl chloride, acrylic polymer, polyacrylonitrile, polyimide, polyamide, It may be made of one or more selected from the group consisting of cellulose, aramid, nylon, polyester, polyparaphenylenebenzobisoxazole, polyarylate, and Teflon, among which tensile strength, rigidity, surface hardness, abrasion resistance, and heat resistance. It is particularly preferable to include polypropylene (PP), which has excellent mechanical properties and chemical properties such as corrosion resistance.
  • PP polypropylene
  • the sealant layer 30 is polypropylene, cast polypropylene (CPP), acid modified polypropylene, polypropylene-butylene-ethylene copolymer, or a combination thereof. It may include.
  • the sealant layer 30 may have a single-layer structure or a multi-layer structure including two or more layers made of different polymer materials.
  • the sealant layer may have a total thickness of 60 ⁇ m to 100 ⁇ m, preferably 60 ⁇ m to 90 ⁇ m, more preferably 70 ⁇ m to 90 ⁇ m. If the thickness of the sealant layer is too thin, sealing durability and insulation may be reduced, and if it is too thick, flexibility may decrease and the total thickness of the pouch film laminate may increase, resulting in a decrease in energy density relative to volume.
  • the pouch film laminate 1 can be manufactured through a pouch film laminate manufacturing method known in the art.
  • the base layer 10 is attached to the upper surface of the barrier layer 20 through an adhesive
  • the sealant layer 30 is attached to the lower surface of the barrier layer 20 through coextrusion or adhesive. It can be manufactured through a forming method, but is not limited to this.
  • the pouch 100 is manufactured by inserting the pouch film laminate as described above into a molding device and applying pressure to a portion of the pouch film laminate with a punch to form a cup portion.
  • the pressure may be 0.3 MPa to 1 MPa, preferably 0.3 MPa to 0.8 MPa, and more preferably 0.4 MPa to 0.6 MPa. If the pressure is too low when molding the cup portion, excessive drawing may occur and wrinkles may occur, and if it is too high, drawing may not occur well and the molding depth may be reduced.
  • the moving speed of the punch may be 20 mm/min to 80 mm/min, preferably 30 mm/min to 70 mm/min, and more preferably 40 mm/min to 60 mm/min. If the pressure during molding is too small or the moving speed of the punch is too fast, wrinkles may occur due to buckling. If the pressure during molding is too large or the moving speed of the punch is too slow, cup corners may appear during molding. As the stress concentrated in increases, the occurrence of pinholes or cracks may increase.
  • the pouch 100 of the present invention manufactured through the method described above includes a lower case 101, an upper case 102, and a folding portion 130 connecting the lower case and the lower case.
  • the lower case includes a cup portion 110 that is indented in one direction.
  • the pouch 100 may have a 1-cup shape with the cup portion 110 formed only in the lower case 101, but is not limited thereto, and includes the upper case and It may be a two-cup type with cup portions formed on both lower cases.
  • the upper case is folded so that the cup portion of the upper case and the cup portion of the lower case face each other, so it can accommodate a thicker electrode assembly than a 1-cup pouch. This has the advantage of being advantageous in realizing high energy density.
  • the cup portion 110 has a receiving space for accommodating the electrode assembly 200.
  • the pouch 100 may include a terrace 120 around the cup portion 110.
  • the terrace 120 refers to the unmolded portion of the pouch film laminate, that is, the remaining area excluding the cup portion 110.
  • the terrace 129 is a part that is sealed through thermal bonding in the process of accommodating the electrode assembly 200 in the cup portion 110, injecting electrolyte, and then sealing.
  • the cup portion 110 may include a bottom surface and a peripheral surface.
  • the peripheral surface may connect the floor surface and the terrace 120.
  • the bottom surface may cover one side of the electrode assembly 200, and the peripheral surface may surround the circumference of the electrode assembly 200.
  • the folding part 130 connects the lower case 101 and the upper case 102, stores the electrode assembly 200 in the cup part 110, and folds after injecting the electrolyte to form the upper case 102. It is possible to seal the cup portion 110 of the lower case 101.
  • the folding part 130 is included, the lower case 101 and the upper case 102 are integrally connected, so when performing a sealing process later, the number of sides to be sealed is reduced, thereby improving fairness.
  • the folding part 130 is formed to be spaced apart from the cup part 110, and the separation distance between the folding part 130 and the cup part 110 may be about 0.5 mm to 3 mm, preferably about 0.5 mm to 2 mm. If the folding part 130 is formed too close to the cup part 110, folding is not performed smoothly, and if the folding part 130 is formed too far from the cup part 110, the total volume of the secondary battery increases and the energy density relative to volume increases. may decrease. In the case of a 2-cup case, the folding portion may be formed to satisfy the above-mentioned separation distance for each cup portion.
  • the electrode assembly 200 may include a plurality of electrodes and a plurality of separators that are alternately stacked.
  • the plurality of electrodes are alternately stacked with a separator in between and may include an anode and a cathode having opposite polarities.
  • the electrode assembly 200 may be provided with a plurality of electrode tabs 230 welded to each other.
  • the plurality of electrode tabs 230 may be connected to the plurality of electrodes 210 and may protrude outward from the electrode assembly 200 to act as a path through which electrons can move between the inside and outside of the electrode assembly 200. there is.
  • a plurality of electrode tabs 230 may be located inside the pouch 100.
  • the electrode tab 230 connected to the anode and the electrode tab 230 connected to the cathode may protrude in different directions with respect to the electrode assembly 200. However, it is not limited to this, and it is possible for the electrode tab 230 connected to the anode and the electrode tab 230 connected to the cathode to protrude in the same direction and parallel to each other.
  • Leads 240 that supply electricity to the outside of the secondary battery may be connected to the plurality of electrode tabs 230 by spot welding or the like. One end of the lead 240 may be connected to the plurality of electrode tabs 230 and the other end may protrude to the outside of the pouch 100 .
  • a portion of the lead 240 may be surrounded by an insulating portion 250 .
  • the insulating portion 250 may include an insulating tape.
  • the insulating portion 250 may be located between the terrace 120 of the first case 101 and the second case 102, and in this state, the terrace 120 and the second case 102 are opened to each other. can be fused.
  • a portion of the terrace 120 and the second case 102 may be heat-sealed to the insulating portion 250. Accordingly, the insulating portion 250 prevents electricity generated from the electrode assembly 200 from flowing into the pouch 100 through the lead 240 and maintains the seal of the pouch 100.
  • the electrode assembly 200 may have a ratio of the full length to the full width length of 5 to 10, preferably 5 to 8.
  • the ratio of total length to total width satisfies the above range, high energy density can be achieved in a limited space.
  • the electrode assembly may have an overall length of 400 mm to 600 mm and an overall width of 50 to 150 mm, preferably 500 mm to 600 mm in overall length, and 50 to 100 mm in overall width.
  • the weight of the electrode assembly may be 500 g to 1500 g, preferably 550 g to 1450 g, and more preferably 600 g to 1400 g.
  • the weight of the electrode assembly satisfies the above range, high capacity can be realized, and the friction between the electrode assembly and the inner surface of the battery case increases, resulting in excellent impact resistance.
  • the secondary battery according to the present invention may further include at least one fixing member on the outer surface of the electrode assembly, if necessary.
  • the electrode assembly is used to prevent the alignment of the components of the electrode assembly, that is, the anode, cathode, and separator, from being disturbed.
  • a fixing member that secures the assembly by wrapping it in the full width direction can be used.
  • the fixing member may include a porous structure.
  • the electrolyte can pass through the fixing member and be impregnated into the electrode assembly, thereby preventing the electrolyte impregnation of the electrode assembly from being deteriorated due to the fixing member.
  • the fixing member may be a finishing tape with an adhesive layer formed on one side of a polymer base layer having a porous structure, but is not limited thereto.
  • the polymer material may be, for example, polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyethylene (PE), etc., but is not limited thereto.
  • the fixing member preferably has a width of about 10 to 50 mm or 20 to 40 mm along the full width direction of the electrode assembly. If the width of the fixing member is too wide, the outer surface area of the electrode assembly covered by the fixing member increases and the contact area with the electrolyte decreases, which may reduce electrolyte impregnation and reduce the friction between the electrode assembly and the battery case. Impact resistance may decrease. On the other hand, if the width of the fixing member is too thin, the effect of fixing the electrode assembly may be reduced.
  • the secondary battery may include 2 to 10 fixing members, preferably 2 to 8 fixing members, and more preferably 3 to 7 fixing members.
  • the fixing members may be arranged in left and right symmetrical positions along the overall length direction, and preferably, the fixing members may be spaced apart at equal intervals.
  • the contact area between the fixing member and the electrode assembly may be 30% or less, 25% or less, or 20% or less of the total surface area of the electrode assembly.
  • the contact area between the fixing member and the electrode assembly may be 0 to 30%, 1 to 30%, 5 to 30%, 5 to 25%, or 5 to 20% of the total surface area of the electrode assembly. .
  • the contact area between the fixing member and the electrode assembly can be adjusted by adjusting the width of the fixing member used or the number of fixing members used. Since the commonly used fixing member is made of a material with a lower friction coefficient than the separator disposed on the outermost surface of the electrode assembly, if the area of the fixing member surrounding the electrode assembly increases, the friction between the electrode assembly and the inner surface of the battery case will decrease. You can. Therefore, when using a fixing member, it is desirable to suppress a decrease in friction force by setting the contact area between electrode assemblies to 30% or less.
  • the electrolyte is used to move lithium ions generated by the electrochemical reaction of the electrode during charging and discharging of the secondary battery, and may include an organic solvent and a lithium salt.
  • the organic solvent may be used without particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • the organic solvent includes ester solvents such as methyl acetate, ethyl acetate, ⁇ -butyrolactone, and ⁇ -caprolactone; Ether-based solvents such as dibutyl ether or tetrahydrofuran; Ketone-based solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethylcarbonate (DMC), diethylcarbonate (DEC), methylethylcarbonate (MEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate Carbonate-based solvents such as PC); Alcohol-based solvents such as ethyl alcohol and isopropyl alcohol; nitriles such as R-CN (R is a C2 to C20 straight-chain, branched or
  • carbonate-based solvents are preferable, and cyclic carbonates (e.g., ethylene carbonate or propylene carbonate, etc.) with high ionic conductivity and high dielectric constant that can improve the charge/discharge performance of the battery, and low-viscosity linear carbonate-based compounds ( For example, ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate, etc.) are more preferable.
  • cyclic carbonates e.g., ethylene carbonate or propylene carbonate, etc.
  • low-viscosity linear carbonate-based compounds For example, ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate, etc.
  • the lithium salt can be used without particular limitations as long as it is a compound that can provide lithium ions used in lithium secondary batteries.
  • the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN(C 2 F 5 SO 3 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , LiN(CF 3 SO 2 ) 2 .
  • LiCl, LiI, or LiB(C 2 O 4 ) 2 may be used.
  • the concentration of the lithium salt is preferably used within the range of 0.1 to 5.0M, preferably 0.1 to 3.0M. When the concentration of lithium salt is within the above range, the electrolyte has appropriate conductivity and viscosity, so excellent electrolyte performance can be achieved and lithium ions can move effectively.
  • the electrolyte may further include additives for the purpose of improving battery life characteristics, suppressing battery capacity reduction, and improving battery discharge capacity.
  • a pouch in which nylon/polyethylene terephthalate/Al alloy thin film/polypropylene were sequentially laminated and the cup portion was molded was prepared. After storing the stacked electrode assembly with a total length of 548 mm, a total width of 99 mm, and a weight of 1380 g in the cup part, an electrolyte solution was injected, sealing was performed, and an activation process was performed to manufacture a pouch-type secondary battery. At this time, the electrolyte was injected so that the amount of remaining electrolyte per unit capacity was 2.2 g/Ah after the activation process.
  • a pouch-type secondary battery was manufactured in the same manner as Example 1, except that the electrolyte was injected so that the amount of remaining electrolyte per unit capacity was 2.15 g/Ah after the activation process.
  • a stacked electrode assembly with a total length of 548 mm, a total width of 78 mm, and a weight of 641 g was used, and the same method as Example 1 was used, except that the electrolyte solution was injected so that the amount of remaining electrolyte per unit capacity was 1.7 g/Ah after the activation process.
  • a pouch-type secondary battery was manufactured.
  • a stacked electrode assembly with a total length of 548 mm, a total width of 78 mm, and a weight of 641 g was used, and the same method as Example 1 was used, except that the electrolyte solution was injected so that the amount of remaining electrolyte per unit capacity was 2.2 g / Ah after the activation process.
  • a pouch-type secondary battery was manufactured.
  • a pouch-type secondary battery was manufactured in the same manner as Example 1, except that the electrolyte was injected so that the amount of remaining electrolyte per unit capacity was 2.3 g/Ah after the activation process.
  • a crash shock test was performed on the pouch-type secondary batteries manufactured in Examples 1 to 3 and Comparative Examples 1 to 2 under crash conditions of 133.7G x 15.8ms. The measurement results are shown in Table 1 below. If electrolyte leakage and electrode assembly separation did not occur after the test, it was marked as Pass, and if electrolyte leakage and/or electrode assembly separation occurred, it was marked as Fail.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne une batterie secondaire ayant une excellente résistance aux chocs. La batterie secondaire selon la présente invention comprend un ensemble électrode, un électrolyte et un boîtier de batterie comprenant une unité de réception pour recevoir l'ensemble électrode et l'électrolyte, et satisfait la formule (1). Dans la formule (1) : W / S ≤ 42(g/Ah)·m-2, W est une quantité d'électrolyte [unité : g/Ah] par capacité unitaire de la batterie secondaire, et S est une multiplication de la longueur totale [unité : m] et de la largeur totale [unité : m] de l'ensemble électrode.
PCT/KR2023/015867 2022-10-14 2023-10-13 Batterie secondaire WO2024080837A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2022-0132745 2022-10-14
KR20220132745 2022-10-14
KR10-2023-0136858 2023-10-13
KR1020230136858A KR20240052696A (ko) 2022-10-14 2023-10-13 이차 전지

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WO2024080837A1 true WO2024080837A1 (fr) 2024-04-18

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100874385B1 (ko) * 2006-07-10 2008-12-18 주식회사 엘지화학 이차전지용 안전부재
KR101300111B1 (ko) * 2011-08-31 2013-08-30 주식회사 엘지화학 수분 침투에 대한 장기 신뢰성이 향상된 이차 전지
CN109952664A (zh) * 2016-10-26 2019-06-28 大日本印刷株式会社 电池用包装材料、其制造方法、电池及其制造方法
KR20190142246A (ko) * 2018-06-15 2019-12-26 스미또모 가가꾸 가부시키가이샤 비수 전해액 이차 전지용 다공질층
KR20220047107A (ko) * 2020-10-08 2022-04-15 주식회사 엘지에너지솔루션 개선된 고정성을 가지는 파우치형 전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100874385B1 (ko) * 2006-07-10 2008-12-18 주식회사 엘지화학 이차전지용 안전부재
KR101300111B1 (ko) * 2011-08-31 2013-08-30 주식회사 엘지화학 수분 침투에 대한 장기 신뢰성이 향상된 이차 전지
CN109952664A (zh) * 2016-10-26 2019-06-28 大日本印刷株式会社 电池用包装材料、其制造方法、电池及其制造方法
KR20190142246A (ko) * 2018-06-15 2019-12-26 스미또모 가가꾸 가부시키가이샤 비수 전해액 이차 전지용 다공질층
KR20220047107A (ko) * 2020-10-08 2022-04-15 주식회사 엘지에너지솔루션 개선된 고정성을 가지는 파우치형 전지

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